Chromenopyrazol and process for preparation thereof

ABSTRACT

Chromenopyrazol compounds having the formula   D R A W I N G

United States Patent Kimura et al.

[ 1 Oct. 10,1972

[72] Inventors: Shiro Kimura; Sadao Ishige; Teruo Kobayashi, all of Kanagawa, Japan [73] Assignee: Fuji Photo Film Co., Ltd.,

Kanagawa, Japan 221 Filed: Sept. 16, 1969 l2l I Appl. No.: 858,522

[30] Foreign Application Priority Data Sept. 16, 1968 Japan ..43/66822 [52] US. Cl. ..260 /310 R, 117/36.8, 260/310 A, 2'60/519 [51] Int. Cl. ..C07d 49/18 [58-] Field of Search ..260/3 10 R [56] References Cited FOREIGN PATENTS OR APPLlCATlONS 43/1 [,244 6/1965 Japan ..260/3l0 R OTHER PUBLICATIONS Beilstein Handbuch der Organischen Chemie 4th ed., 1st Supplement, Vols. 26- 7, pages 666- 7. Berlin, Springer, 1938. QD251.B4

Lagidze et al. Chem. Abst. Vol. 68, No. 68768r (1968). QDLASI Patterson et al. The Ring Index 2nd ed. page 757 (No. 5485) Wash, DC, Amer. Chem. Soc., 1960. QD29LP3.

Chemical Abstracts Vol. 72, Subject Index, P- Z, page 3,558 s (1970) QDLASl Primary ExaminerNatalie Trousof Attorney-Sughrue, Rothwell, Mion, Zinn & Macpeak ABSTRACT Chromenopyrazol compounds having the formula MY C\ 0 and a process for their preparation are disclosed. The Chromenopyrazol compounds are useful as couplers in pressure-sensitive duplicating papers.

11 Claims, No Drawings CHROMENOPYRAZOL AND PROCESS FOR PREPARATION THEREOF DESCRIPTION OF THE INVENTION novel lactone compound of chromenopyrazol having the following Formula (III) 2- N g z/ wherein each R and R is selectedfrom the group consisting of an alkyl group having from one to five carbon atoms, and a benzyl group, wherein X is selected from the group consisting of an alkyl group having from one to five carbon atoms, an aryl group and a substituted aryl group, and wherein Y is selected from the group consisting of an alkyl group having one to 17 carbon atoms, an aryl group, substituted aryl group, an amino group, an acylamino group, a carbamoyl group and an alkoxy group having from one to five carbon atoms. This invention also relates to a process for the preparation thereof by condensing a 2-(4-N,N-disubstituted amino-2-hydroxybenzoyl) benzoic acid having the Formula'fl),

R1 0 Q Q 112 H O OH (I) with a l-substituted-3-substituted-5-pyrazolone derivative having the Formula (II),

I N N wherein R R X and Y are as described above.

The aryl group represented by X or Y in above Formulae (II) and (III) can be an unsubstituted phenyl or naphthyl group or a substituted phenyl or naphthyl group with the substitution being by group other than a hydrogen ion-isolating group, such as a sulfo group, a carboxyl group, a hydroxyl group, and the like. For example, suitable substituted phenyl or naphthyl groups are those substituted by an alkyl group, a halogen atom, an alkoxy] group, an acetoxyl group, an amino group, an acylamino group, an acyl group, or a nitro group.

The term chromenopyrazol as used in the present invention describes a compound represented by the formula,

wherein R R,, X and Y are as described above.

The compounds, represented by the Formula I, suitable for use in the process described herein, are exemby 2-(4 N,N-diethylamino-2'-hydroxybenzoyl)benzoic acid, 2-(4'-N,N-dimethylamino-2'- hydroxybenzoyl)benzoic acid, 2(4'-N,N-diamylamino- 2-hydroxybenzoyl)benzoic acid, 2-(4"N-benzyl-N- methylamino-Z'-hydroxybenzoyl)benzoic acid, and the like. These compounds can be prepared by heating phthalic anhydride and the corresponding maminophenol derivatives in toluene according to the method described in Friedlander, Fortschritte der Teerfarbenfarbikation und Verwandter Industriezwiege Vol.IV,p.260 wherein German Pat. Specification No. 85,931 is abstracted. In said specification it is revealed that by heating phthalic anhydride and maminophenol derivative in toluene, benzene, or xylene to boiling for about 8-10 hours, cooling, and recovering the precipitate which is then recrystallized. The phthalic anhydride and dislkyl-m-aminophenol derivatives are present in approximately equal weight amounts and sufficient solvent is used in order to effect a complete dissolution.

The compound represented by the Formula II can be represented also by the formula (IIa) shown as follows:

Y (Il heptadecyl-l-(p-phenoxyphenyl)pyrazolone, 3-(mnitrophenyl l -phenylpyrazolone, 3-methyll (2 ',6 dichloro-4'-methoxyphenyl)pyrazolone, 3-( mnitrophenylcarbamoyl)aminol -(2 6 '-dichloro-4 methoxyphenyl pyrazolone, and the like. These compounds are all known compounds.

The process of the present invention is carried out by reacting the above two materials in a condensation and dehydration reaction. That is, equal molar amounts of the compound represented by Formula (I) and the compound represented by Formula (II) are condensed in a condensation reaction medium, such as sulfuric acid of above 60 percent in concentration, at 30 to 100 C. forfrom 1' to 24 hours. Suitable as condensation reaction media are also phosphoric anhydride, polyphosphoric acid, anhydrous zinc chloride, phosphorous oxychloride, fuming sulfuric acid, in combination with sulfuric acid. Sulfuric acid is preferred as the condensation reaction medium. The reaction medium containing the condensation product of compound. (1) and compound (11) is poured into a large amount of ice water, to precipitate the product, the precipitated product is filtered, and treated with anaqueous alkaline solution to obtain the compound of the Formula (111) as a colorless crystal.

That the compound obtained by the process described above hasa molecular structure represented by the Formula (III) was confirmed by means of an infrared absorption spectrum and elemental analysis. That is, with these compounds, the characteristic absorption of carbonyl group in the lactone ring isnear 1,755 cm. with the characteristic absorptions of carboxyl group and hydroxyl group in the Formula (I) and Formula ,(II) not being observed. (However, in the compounds .prepared in Examples 9 and 13, the characteristic absorption of the carbonyl group in the amide group was observed.) The results of elemental analysis was identical with the theoretical value.

The lactam of chromenopyrazole prepared as above and represented by the above Formula (1) is a novel compound.'lt is useful as a coupler for use in pressuresensitive duplicating papers, heat-sensitive duplicating papers, coupler inks and the like, because, the lactone of chromenopyrazole, a colorless compound, develops a yellowish-orange to reddish-orange color on contact with a solid acid, an organic acid, or phenols.

EXAMPLE I Preparation of the Lactone of 7-N,N-dimethylamino-4- (O-carboxyphenyl )-4-hydroxyl -phenyl-3 -methyl- 1 ,4- dihydrochromeno 2,3-C] pyrazol \N 0 N N 0 163 c MOE:

hydroxybenzoyl)benzoic acid and 8.7 g. (1/20 mole) of 3-methyl-l-phenyl-5-pyrazolone were dissolved in 72 g. of 94 m 96 percent concentrated sulfuric acid; at a temperature of below 45 C., thereafter heated to a temperature of 90 1 2 C. for 3 hours, and cooled to ambient temperature. The reaction solution was poured into 800 g. of ice water and the precipitate was filtered. This precipitate was extracted with 600 ml. of

EXAMPLE II Preparation of the Lactone of 7-N,N-diethylamino-4- (o-carboxyphenyl)-4-hydroxyl -phenyl-3-methyl-l 1 ,4- dihydrochromeno [2,3-C1pyrazol.

15.7 g. (1/20 mole) of 2-(4'-N,N-diethylamino-2'- hydroxybenzoyl)benzoic acid and 8.7 g. (l/20 mole) of 3-methyl-l-phenyl-5-pyrazolone were reacted (at C. for 20 hours) and treated as in Example 1 to obtain 19.5 g. of a colorless crystal melting at 26026 1 C.

Elemental analysis for C,,H,,,N,O,:

Found: C 74.23; H 5.57; N 9.37

Calculated: C 74.48; H 5.58; N 9.31. 0 The product was adsorbed on acid clay and developed a yellowish-orange color.

EXAMPLE III Preparation of the Lactone of 7-N-benzyl-N- ethylamino-4-(o-carboxyphenyl)-4-hydroxy-l-phenyl- 3-methyl-1 ,4-dihydrochromeno [2,3-C] pyrazol.

18.8 g. (l/20 mole) of 2-(4'-N-benzyl-N-ethylamino- 2'-hydroxybenzoyl) benzoic acid and 8.7 g. (l/20 mole) of 3-methyl-l-phenyl-S-pyrazolone were dissolved in g. of 98 percent sulfuric acid at a temperature of below 40C. 5 g. of phosphoric anhydride were added and the mixture heated to 60 C. for 4 hours, the procedure of Example 1 was then followed and 21.4 g. of a colorless crystal melting at 198- 202 C. was obtained.

Elemental analysis for C H N O The product was adsorbed on acid clayand developed Experiments Found: C 77.21; H 5.18; N 8.64

Calculated: C 76.93; H 5.04; N 8.41.

orange color.

chromenopyrazol compounds in the following table, and represented by Formula (111) above, prepared by condensing a benzoic acid derivative of the Formula v xm The Analysis obtained on the chromenopyrazole compounds prepared are shown in column 6.

Example number R1 Characteristics 9 CzHs 1U CzHg,

Cg H

CgH5

Cl CH Same as above. 0C H Same as above. NH

Analysis for CH21N303: Found-C, 74.68; H, 5.78; N, 9.10,

Calculated-C, 74.82; H, 5.85; N, 9.03,

Developed color tone: Yellowish-orange.

Analysis for CgBHzQClZNQOQ: FoundC, 60.70; H, 4. 7.968; 01, 18.98. Calculated0, 60.61; H, 4.00; N, 7 l

17. Developed color tone: Yellowish-orauge.

M.P.: 178-180" C. Analysis for CzwHzrClaNzOz: FoundC, 59.48; H 4.

Cl, 18.07. Calculated-C, 69.55; H, 4.13; N, 7.18; C],

Developed color tone: Yellowish-orange.

M.P.: 205 C.

Analysis for C33H21N303: Found-C, 77.14; H, 5.26; N, 8.27,

Calculated-C, 77.17; H, 6.30; N, 8.18.

Developed color tone: Orange.

M.P.: 265-267 C.

Analysis for C11H24N403FO11I1d-C, 71.48; H, 5.40; N, 12.47,

Calculated0, 71.66; H, 5.35; N, 12.38. Developed color tone: Yellowish-red.

M.P.: 264-260 C Analysis for C H ClN 04: Found-C,

9.63; Cl, 5.89. Calculated-C, 69.09; H,

6.00. Developed color tone: Reddish-orange.

68.88; H 4.49; N, 4.60; N, 9.48; C],

Recrystallized from a benzene-ether mixed solvent.

Analysis for CzaHzaNaOaZ Found-C, 70.81; H, 6.01; N, 10.77.

Calculated-C, 70.93; H, 5.95; N, 10.79.

Developed color tone: Yellowish-orange.

Colorless syrup.

ysis for CH51N304ZFO11I1dC, 78.06; H, 7.89; N, 5.41.

Ca1enlated0, 78.24; H, 7.95; N, 6.48.

Developed color tone: Orange.

)unnx. of coupler solution in acetic acid: 505 my and M.P.: Above 300 0.

Analysis for C31HggN405IF011I1dC, 69.97; H, 4.23; N,-10.51.

Calcu1atedC, 70.18; H, 4.18; N, 10.56.

Developed color tone: Yellowish-orange.

Example number R R X Y Qharacteristics 13 C C H OCH NH M.P.: 287-290 0.

2 2 l a 1 Analysis for C35HZ5CI2N601: Found-C, 58.82; H, 3.98; N,

0:0 11.67. Calculated-C. 58.74; H, 3.94; N, 11.75.

| Developed color tone: Reddish-orange. NH

' (n-Heptadecyl) We claim: where each R and R, is selected from the group conlwA process for preparing a chromenopyrazol compound of claim 8, which comprises condensing in a condensation reaction medium a 2-(4'-N,N-disubstituted amino-2-hydroxybenzoyl) benzoic acid having the formula:

wherein X and Y are as defined in claim 8, said 2-(4'- N,N-disubstituted amino-2'-hydroxybenzoyl)benzoic acid and said pyrazolone derivative being present in said condensing reaction medium in equal molar amounts for l to 24. hours at 30 to 100 C., said condensation reaction medium being selected from the group consisting of sulfuric acid of above 60 percent in concentration and sulfuric acid and a member selected from the group consisting of phosphorous anhydride, polyphosphoric acid, anhydrous zinc phosphorous oxychloride, and fuming sulfuric acid.

2. The process of claim 1, wherein said:2-(4'-N,N-- disubstituted amino-2'-hydroxybenzyl)benzoic acid is selected form the group consisting of 2-(4'N,N- diethylamino-2'-hydroxy-benzoyl)benzoic acid, 2-(4- N,N-diamylamino-2f-hydroxybenzoyl) benzoic acid, 2- (4'-N,N-dimethylamino-2-hydroxybenzoyl)benzoic acid, and 2-(4-benzyl-N-methylamino-2'-hydroxybenzoyl)benzoic acid.

3. The process of claim 1 wherein said pyrazolone derivative is selected from the group consisting of 3- methyl?l-phenylpyrazolone, 3-methyl-l-(ptolyl )pyrazolone, 3-ethoxyl 2 ,4 ,6 'yl )pyrazolone, phenylpyrazolone, 3-(p-chlorobenzoyl)amino-l-phenylpyrazolone, 1,3-dimethylpyr21zolone, 3-heptadecyl-l (p-phenoxyphenyl)pyrazolone, 3-(m-nitrophenyl)- l phenylpyrazolone, B-methyl-l-(2',6'-dichloro-4- dichloro-4-methoxyphenyl)pyrazolone.

4. A chromenopyrazol compound having the chloride,

sisting of alkyl of from one to five carbon atoms and benzyl, wherein X is selected from the group consisting of alkyl of one to five carbon atoms; phenyl; naphthyl; substituted phenyl, said substituents being selected from the group consisting of lower alkyl, halogen, nitro, lower alkoxyl and phenoxy; and substituted naphthyl said substituents being selected from the group consisting of lower alkyl, halogen, nitro and lower alkoxyl; and wherein Y is selected from the group consisting of alkyl of from one to l7 carbon atoms; alkoxyl of from one to five carbon atoms; phenyl; naphthyl; nitro phenyl, nitrosubstituted naphthyl, amino, pchlorobenzoylamino, and m-nitrophenyl-carbamoylamino.

5. The compound of claim 4, wherein said R and R are methyl, X is phenyl, and Y is selected from the group consisting of methyl and nitrophenyl.

6. The compound according to claim 4, wherein said R, is ethyl, said R, is phenylethyl, X is phenyl, and Y is methyl.

7. The compound according to claim 4, wherein said R, and R, are ethyl, X is selected from the group consisting of methyl and methylphenyl, and Y is methyl.

8. The compound according to claim 4, wherein'said R and R, are ethyl, X is trichlorophenyl, and Y is selected from the group consisting of methyl and ethox- 9. The compound according to claim 4, wherein said R, and R, are ethyl, said X is phenyl, and said Y is selected from the group consisting of phenyl, amino, pchlorobenzoylamino, and methyl.

10. The compound according to claim 4, wherein said R and R are ethyl, X is and Y is C I- 1 1,. The compound according to claim 4, wherein said R and R are ethyl, is

OCH;

v (HQ-CL and Y is nitrophenylcarbamoylamino. 

2. The process of claim 1, wherein said 2-(4''-N,N-disubstituted amino-2''-hydroxybenzyl)benzoic acid is selected form the group consisting of 2-(4''N,N-diethylamino-2''-hydroxy-benzoyl)benzoic acid, 2-(4''-N,N-diamylamino-2''-hydroxybenzoyl) benzoic acid, 2-(4''-N,N-dimethylamino-2''-hydroxybenzoyl)benzoic acid, and 2-(4''-benzyl-N-methylamino-2''-hydroxybenzoyl)benzoic acid.
 3. The process of claim 1 wherein said pyrazolone derivative is selected from the group consisting of 3-methyl-1-phenylpyrazolone, 3-methyl-1-(p-tolyl)pyrazolone, 3-ethoxy-1-(2'', 4'',6'' -trichlorophenyl)pyrazolone, 1,3-diphenylpyrazolone, 3-amino-1-phenylpyrazolone, 3-(p-chlorobenzoyl)amino-1-phenylpyrazolone, 1,3-dimethylpyrazolone, 3-heptadecyl-1-(p-phenoxyphenyl)pyrazolone, 3-(m-nitrophenyl)-1-phenylpyrazolone, 3-methyl-1-(2'',6'' -dichloro-4''-dichloro-4''-methoxyphenyl)pyrazolone.
 4. A chromenopyrazol compound having the
 5. The compound of claim 4, wherein said R1 and R2 are methyl, X is phenyl, and Y is selected from the group consisting of methyl and nitrophenyl.
 6. The compound according to claim 4, wherein said R1 is ethyl, said R2 is phenylethyl, X is phenyl, and Y is methyl.
 7. The compound according to claim 4, wherein said R1 and R2 are ethyl, X is selected from the group consisting of methyl and methylphenyl, and Y is methyl.
 8. The compound according to claim 4, wherein said R1 and R2 are ethyl, X is trichlorophenyl, and Y is selected from the group consisting of methyl and ethoxy.
 9. The compound according to claim 4, wherein said R1 and R2 are ethyl, said X is phenyl, and said Y is selected from the group consisting of phenyl, amino, p-chlorobenzoylamino, and methyl.
 10. The compound according to claim 4, wherein said R1 and R2 are ethyl, X is
 11. The compound according to claim 4, wherein said R1 and R2 are ethyl, X is 